The reaction of [NiCl2(PMe2Ph)(2)] with fc(SH)(2) (fcS(2) = 1,1'-ferrocenedithiolato) afforded the Ni-Fe heterobimetallic complex containing an Fe-->Ni dative bond [Ni(S(2)fc)(PMe2Ph)] (1) with concurrent liberation of one of the PMe2-Ph ligands. In contrast, similar treatment of [MCl2(dppe)] (M = Ni, Pd, Pt; dppe = Ph2PCH2CH2PPh2) gave a series of group 10 metal-ferrocenedithiolato complexes [M(S(2)fc)(dppe)] (2) which do not contain such a dative bond. Furthermore, oxidation of complexes 2 with 1 equiv of [(eta(5)-C5H5)(2)Fe][PF6] resulted in the formation of 1,1'-ferrocenedithiolato-bridged complexes [{M(dppe)}(2)(mu-S(2)fc)][PF6](2) (3) along with poly(1,1'-ferrocenylene disulfide). Complexes 2 were also converted into the Fe-Ru-M heterotrimetallic complexes [(p-cymene)RuCl-(mu-S(2)fc)M(dppe)][PF6] (4; p-cymene = 4-isopropyltoluene) by the reaction of 2 with [(p-cymene)RuCl2](2) and NH4PF6 in acetonitrile. The detailed structures of 1, [Ni(S(2)fc)(dppe)] (2a), [Pd(S(2)fc)(dppe)] (2b), [{Ni(dppe)}(2)-(mu-S(2)fc)][PF6](2) (3a), and [(p-cymene)RuCl(mu-S(2)fc)Ni(dppe)][PF6] (4a) have been determined by X-ray crystallography.